EP1669407B1 - Mélanges transparents de copolymères à blocs du type styrène-butadiène - Google Patents

Mélanges transparents de copolymères à blocs du type styrène-butadiène Download PDF

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EP1669407B1
EP1669407B1 EP05025845A EP05025845A EP1669407B1 EP 1669407 B1 EP1669407 B1 EP 1669407B1 EP 05025845 A EP05025845 A EP 05025845A EP 05025845 A EP05025845 A EP 05025845A EP 1669407 B1 EP1669407 B1 EP 1669407B1
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range
dienes
block copolymers
ratio
mol
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EP1669407A1 (fr
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Konrad Dr. Knoll
Daniel Dr. Wagner
Jürgen Dr. Koch
Peter Merkel
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the invention relates to mixtures comprising linear block copolymers made from vinylaromatic monomers and dienes of the structure (I) S 1 -B 1 -S 2, and (II) B 2 -S 3 wherein S 1 is a block of vinylaromatic monomers having a number average Mplmasse M n in the range from 40,000 to 100,000 g / mol, S 2 and S 3 respectively for blocks of vinylaromatic monomers having a number average molecular weight M n in the range of 5,000 to 20,000 g / mol, B 1 and B 2 each for blocks of dienes or copolymer blocks Serve and vinyl aromatic monomers having a number average molecular weight M n in the range of 15,000 to 100,000 g / mol, and the ratio of the block copolymers (I) / (II) is in the range of 0.5 to 10. Furthermore, the invention relates to processes for the preparation of the mixtures and their partial or complete hydrogenation.
  • Tough, transparent materials based on anionic polymerized styrene-butadiene block copolymers are known and established in the market for extrusion and injection molding applications.
  • the block copolymers can be linear or star-shaped.
  • the star-shaped block copolymers usually prepared by coupling are achieved by two or more times initiating an asymmetric structure.
  • Linear styrene-butadiene block copolymers are usually only initiated in a simple manner. By appropriate monomer sequence an asymmetrical structure can be achieved.
  • a long, external styrene block causes a certain compatibility of the block copolymer with standard polystyrene. Therefore, these block copolymers can be blended with the cheaper standard polystyrene in amounts of 10 to 70 wt .-%, based on the blend to increase the rigidity.
  • the transparency decreases and, at the same time, turbidity (haze) occurs.
  • Standard polystyrene optical properties are generally unfavorable.
  • Styrene-butadiene block copolymers and blends with polystyrene are known with a variety of structures.
  • the block copolymers can be linear or star-branched and have blocks of identical or different molecular weights, resulting in symmetrical and asymmetrical structures.
  • the butadiene-containing blocks may also contain styrene. Sharp or smeared transitions can occur between blocks.
  • An overview of styrene-butadiene block copolymers can be found, for. In Kunststoff Handbuch, Vol. 4 Polystyrene, Carl Hanser-Verlag Kunststoff-Munich 1996, chapter 3.3.4, pages 161-164 ,
  • the US 5,227,419 describes mixtures of block copolymers whose butadiene-containing blocks have a styrene gradient. In the mixture, the block copolymer with the higher styrene block content is also present in a minor amount.
  • copolymers described in mixtures with polystyrene with comparable toughness lead to a drastic reduction in rigidity over that of polystyrene.
  • the heat resistance is significantly reduced.
  • the WO 00/58380 describes inter alia linear block copolymers having improved toughening efficiency, which have a random copolymer block of styrene and butadiene.
  • the mixtures mentioned can under certain processing conditions, eg. B. segregate at too long residence at 200 ° C without shearing and thus lead to turbidity.
  • the object of the invention was to remedy the disadvantages mentioned and to provide transparent mixtures of styrene-butadiene block copolymers, which have a high toughness and good transparency in blends with polystyrene even at higher polystyrene.
  • the ratio of the block copolymers (I) / (II) is in the range of 0.5 to 10, preferably in the range of 1 to 5, particularly preferably in the range of 2 to 3.
  • Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ring-alkylated styrenes such as p-methylstyrene or tert-butylstyrene, or 1,1-diphenylethylene or mixtures thereof.
  • Preferred dienes are butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene or piperylene or mixtures thereof; particularly preferred are butadiene and isoprene.
  • Particularly preferred block copolymers are formed from the monomers styrene and butadiene.
  • the blocks B 1 and B 2 may be composed exclusively of dienes or of dienes and vinylaromatic monomers.
  • the ratio vinylaromatic monomer / diene is usually in the range of 0 to 2 for the blocks B 1 and B 2 , wherein in the blocks B 1 and B 2 may be the same or different vinyl aromatic monomer / diene ratios.
  • blocks B 1 and B 2 are homopolydiene blocks, especially homopolybutadiene blocks or copolymer blocks having a vinyl aromatic monomer / diene ratio in the range of 0.3 to 1.5.
  • the copolymer blocks have a random distribution of the diene and vinyl aromatic monomers.
  • the number-average molar masses M n of S 1 are in the range from 40,000 to 100,000 g / mol, preferably in the range from 60,000 to 85,000, particularly preferably in the range from 70,000 to 80,000.
  • the number-average molar masses M n of S 2 and S 3 in each case and independently of one another are in the range from 5,000 to 20,000 g / mol, preferably in the range from 8,000 to 17,000 g / mol, particularly preferably in the range from 11,000 to 14,000 g / mol.
  • the blocks B 1 and B 2 of dienes or copolymer blocks of dienes and vinylaromatic monomers each independently have a number average molecular weight Mn in the range of 15,000 to 100,000 g / mol, preferably in the range of 50,000 to 75,000 g / mol, more preferably in the range of 60,000 to 70,000 g / mol.
  • the block copolymers (I) are preferably of asymmetrical construction, ie the blocks S 1 and S 2 have different number-average molar masses M n , preferably with a ratio of the number-average molar masses of S 1 to S 2 of at least 2, preferably in the range of 5 - 8th.
  • the mixtures according to the invention can be prepared by preparing the block copolymers (I) and (II) in each case by sequential anionic polymerization of vinylaromatic monomers and dienes with alkali metal organic initiators successively or in different reactors and then in the ratio (I) / (II) in the range of 0.5 to 10 are mixed.
  • Preferred block copolymers according to the invention can be formed, for example, by sequential anionic polymerization, wherein at least the polymerization of the soft blocks (B / S) takes place in the presence of a radomizer.
  • the presence of Randomizers cause the statistical distribution of dienes and vinylaromatic units in soft block (B / S).
  • Suitable randomizers are donor solvents, such as ethers, for example tetrahydrofuran, or tertiary amines or soluble potassium salts. In the case of tetrahydrofuran, amounts of generally more than 0.25% by volume, based on the solvent, are used for an ideal statistical distribution. At low concentrations, so-called “tapered" blocks with a gradient in the composition of the comonomers are obtained.
  • the relative proportion of the 1,2-linkages of the diene units increases at the same time to about 30 to 35%.
  • the 1,2-vinyl content in the soft blocks increases only insignificantly.
  • the resulting block copolymers are therefore less susceptible to crosslinking and have a lower glass transition temperature at the same butadiene content.
  • the potassium salt is generally used in molar excess with respect to the anionic polymerization initiator. It is preferable to choose a molar ratio of anionic polymerization initiator to potassium salt in the range from 10: 1 to 100: 1, more preferably in the range from 30: 1 to 70: 1.
  • the potassium salt used should generally be soluble in the reaction medium. Suitable potassium salts are, for example, potassium alkoxides, in particular a potassium alkoxide of a tertiary alcohol having at least 5 carbon atoms.
  • potassium 2,2-dimethyl-1-propoxide potassium 2-methylbutanolate (potassium tertiary amylate), potassium 2,3-dimethyl-3-pentoxide, potassium 2-methylhexoxide, potassium 3, 7-dimethyl-3-octanolate (potassium tetrahydrolinaloolat) or potassium 3-ethyl-3-pentoxide used.
  • the potassium alkoxides are accessible, for example, by reaction of elemental potassium, potassium / sodium alloy or potassium alkylates and the corresponding alcohols in inert solvent.
  • the potassium salt is expediently added to the reaction mixture only after the addition of the anionic polymerization initiator. In this way, hydrolysis of the potassium salt by traces of protic impurities can be avoided. Particularly preferably, the potassium salt is added shortly before the polymerization of the random soft block B / S.
  • the anionic polymerization initiator the usual monofunctional alkali metal alkyls, aryls or aralkyls can be used.
  • organolithium compounds are used, such as ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, diphenylhexyl, butadienyl, isoprenyl, polystyryllithium.
  • the required amount of polymerization initiator depends on the desired molecular weight. In general, it is in the range of 0.001 to 5 mol%, based on the total amount of monomer.
  • the polymerization can be carried out in the presence of a solvent.
  • Suitable solvents are the anionic polymerization customary aliphatic, cycloaliphatic or aromatic hydrocarbons having 4 to 12 carbon atoms such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, iso-octane, benzene, alkylbenzenes, such as toluene, xylene, ethylbenzene or decalin or suitable mixtures , Preferably, cyclohexane and methylcyclohexane are used.
  • the polymerization can also be carried out without solvent.
  • Suitable chain terminators are proton-active substances or Lewis acids, such as water, alcohols, aliphatic or aromatic carboxylic acids and inorganic acids such as carbonic acid or boric acid.
  • the blending of the block copolymers can be carried out at any time after completion of the polymerization, that is, for example, before or after the termination, degassing or other work-up steps.
  • the temporally or spatially separate preparation of the block copolymers (I) and (II) has the advantage that the number-average molar masses M n of the individual blocks S and B can be chosen freely.
  • the block copolymers (I) and (II) can be carried out simultaneously in a reactor by double initiation by sequential anionic polymerization of vinyl aromatic monomers and dienes with alkali metal organic initiators.
  • the joint dosage of initiator I 1 and vinyl aromatic monomers In a first stage, the joint dosage of initiator I 1 and vinyl aromatic monomers and in a second stage after complete conversion of vinylaromatic monomers of the first stage, the joint dosage of initiator I 2 and dienes or dienes and vinyl aromatic monomers.
  • the ratio of the amount of initiator I 1 of the first dose to the amount of initiator I 2 of the second dose is selected in the range of 0.5 to 10. After each metering is polymerized until complete conversion of the monomers.
  • the mixtures obtained by this process each have the same number average molar masses M n for the blocks S 2 and S 3 and the same number average molar masses M n for the blocks B 1 and B 2 .
  • Table 1 Dosing sequence with double initiator dosing step Monomers / initiator educatinged species 1 Initiator (I 1 ) and vinyl aromatic monomer S 1 -I 1 2 Initiator (I 2 ) and diene or diene and vinyl aromatic monomer S 1 -B i -I 1 B 2 -I 2 3 Vinyl aromatic monomer S 1 -B 1 -S 2 -I 1 B 2 -S 3 -I 2 4 Termination reagent, eg isopropanol S 1 -B 1 -S 2 B2-S 3
  • step 2 When using a mixture of diene / vinylaromatic monomer in step 2, by adding Lewis bases such as tetrahydrofuran or potassium salts such as potassium tetrahydrolinaloolate, a statistical distribution of the vinyl aromatic monomers and dienes in blocks B 1 and B 2 can be achieved.
  • Lewis bases such as tetrahydrofuran or potassium salts such as potassium tetrahydrolinaloolate
  • stages 2 and 3 By repeated dosing of dienes or dienes and vinyl aromatic monomers between stages 2 and 3 without re-initiator dosing blocks B 1 and B 2 can be formed, which are composed of several sub-blocks.
  • a mixture of dienes and vinylaromatic monomers is particularly preferably used and, after complete conversion, a mixture of dienes and vinylaromatic monomers having a different ratio of vinylaromatic monomer / diene is metered in and polymerized again.
  • blocks B 1 and B 2 which are each composed of two copolymer blocks (B / S) a and (B / S) b , wherein the ratio vinylaromatic monomer / diene in block (B / S) a in the range from 1 to 1.5 and in the block (B / S) b is in the range of 0.3 to 1.
  • the structures (I) S 1 - (B / S) a - (B / S) b -S 2 and (II) (B / S) a - (B / S) b thus result -S 3 .
  • the mixture according to the invention contains block copolymers having one and two terminal blocks S of vinylaromatic monomers.
  • the amount of the second initiator dosage I 2 should be smaller than the first initiator dosage I 1 .
  • the division of the initiator causes a better compatibility of the mixture according to the invention with standard polystyrene having an average M w in the range of 180,000 to 350,000 g / mol.
  • the initiator ratio I 1 / I 2 is preferably in the range of 0.5 / 1 to 10/1, more preferably in the range of 2/1 to 3/1.
  • the novel mixtures of the linear block copolymers (I) and (II) can be blended with thermoplastic polymers in a wide range.
  • Preferred blends contain 5 to 95 weight percent of the linear block copolymers (I) and (II) and 95 to 5 weight percent of standard polystyrene (GPPS) or impact polystyrene (HIPS).
  • GPPS polystyrene
  • HIPS impact polystyrene
  • Such mixtures can be prepared by compounding during the degassing of the block copolymers, for example by adding polystyrene as a "cold feed" on a vented extruder.
  • the joint workup yields homogeneous ternary mixtures, which can also be used by the processor directly on non-mixing injection molding machines. Alternatively, however, it is also possible to process granulate mixtures on kneaders, extruders or mixing injection molding machines directly into ternary mixtures. In the production of films, the mixture usually takes
  • the mixtures are characterized by high toughness combined with high rigidity. This is manifested, for example, in a higher elongation at break with the same modulus of elasticity compared to conventional styrene-butadiene block copolymer blends with polystyrenes. Therefore, they are particularly suitable for injection molding and allow a material-saving design due to the good toughness / stiffness ratio.
  • the mixtures can be processed into tough moldings, for example transparent hangers, which have a very good dimensional stability even at relatively high temperatures.
  • thermoforming films which can then be thermoformed into cups, lids and lunch boxes and other containers.
  • the high toughness ratio allows the use of thinner films while maintaining strength, which leads to significant material savings.
  • the block copolymer mixtures according to the invention can be modified by partial or complete hydrogenation.
  • the degree of hydrogenation of the olefinic double bonds is 97% and higher
  • the degree of hydrogenation of the vinylaromatic monomers is preferably at least 90%, more preferably at least 95, in particular 98%.
  • the proportion of copolymerized diene units present in the 1,2-vinyl form can be controlled by the addition of substances having donor properties, such as ethers or amines.
  • tetrahydrofuran dimethoxyethane or 2-alkylfurfuryl ether in amounts of from 0.1 to 1% by volume, in particular from 0.25 to 0.5% by volume, based on the hydrocarbon used as solvent, e.g. Cyclohexane.
  • the unsaturated bonds of the diene units and also of the vinylaromatic units of the block copolymer are hydrogenated with a hydrogenation catalyst.
  • a hydrogenation catalyst Preferably, supported hydrogenation catalysts are used.
  • Suitable support materials are, for example, inorganic substrates such as barium sulfate, silicates, carbon or aluminum oxides.
  • Suitable hydrogenation metals are, for example, nickel, cobalt, rhodium, ruthenium, palladium, platinum or other Group 8 metals.
  • the hydrogenation is preferably carried out in a saturated hydrocarbon solvent in which the block copolymer is soluble.
  • a saturated hydrocarbon solvent in which the block copolymer is soluble.
  • Preference is given to cycloaliphatic hydrocarbons, in particular cyclohexane. It makes sense to use the same solvent as in the polymerization, so that the hydrogenation can take place in a process step subsequent to the polymerization.
  • the hydrogenation can be carried out batchwise or continuously, preferably a continuous hydrogenation on a fixed bed catalyst.
  • the hydrogenation is generally carried out at temperatures in the range of 40 ° C to 250 ° C, more preferably in the range of 120 ° C to 180 ° C.
  • the hydrogenation can be carried out at atmospheric pressure to 350 bar, preferably in the range of 100 to 250 bar.
  • Young's modulus, tensile strength and elongation at break were determined according to ISO 527 on stamped standard tensile bars from pressed 1 mm plates. (Press conditions: 200 ° C, 5 min).
  • the transmission measurements were carried out in the range of 400-700 nm on pressed circular disks of the layer thickness 4 mm (pressing conditions: 200 ° C., 5 min).
  • the block copolymer blends were prepared as described in Table 2 by sequential anionic polymerization with double initiator dosage (sec-butyllithium Bu-Li) in step 1 or 2 at a solids content of about 30 wt .-% in cyclohexane at temperatures in the range of 50 -. 80 ° C produced. After completion of the polymerization was quenched with isopropanol and acidified with CO 2 / water. The polymerization was carried out in the presence of potassium tertiary amylate (KTA) at a lithium / potassium molar ratio of 38/1 to obtain a random S / B copolymer block. The block copolymers were freed from solvent on a 16 mm degassing extruder.
  • KTA potassium tertiary amylate
  • the resulting block copolymer blends contain random copolymer block block copolymers of the structure (I) S i - (B / S) a - (B / S) b -S 2 having a number average molecular weight of about 150,000 g / mol and structure (II) (B / S) a - (B / S) b -S 3 with a number average molecular weight of about 75,000 g / mol in the molar ratio (I) / (II) corresponding to the initiator ratio I 1 / I 2 .
  • Example 2 Example 3 1 sec.-BuLi [mol] 27.812 25.65 27.81 Styrene [kg] 2050 1950 2,170.4 KTA [mol] 1,012 1,012 1,012 2a sec.-BuLi [mol] 10.656 12.82 10.66 Butadiene / styrene [kg] 565/785 565/785 519.8 / 752.3 2 B Butadiene / styrene [kg] 685/415 685/415 630.2 / 397.7 3 styrene 500 600 529.6 I 1 / I 2 2.6 / 1 2.1 2.6 / 1
  • the block copolymer blends of Examples 1 to 3 were each containing 60 wt .-% (A), 50 wt .-% (B) and 40 wt .-% (C) polystyrene having an average molecular weight M w of about 270,000 (PS 158 K from BASF Aktiengesellschaft) on a 19 mm twin-screw extruder at 200 ° C.
  • the mechanical and optical values of the blends are summarized in Table 3.
  • Example 3 C Analogously to Examples 1 A to 3 C was a linear styrene-butadiene block copolymer of the structure S 1 - (B / S) 1 - (B / S) 2 -S 2 with random (B / S blocks) according to Example 3 from WO 00/58380 prepared and mixed with 60 wt .-% (A), 50 wt .-% (B) and 40 wt .-% (C) polystyrene PS 158 on a 19 mm twin-screw extruder at 200 ° C.
  • Table 3 Properties of the blends of Examples 1 to 3 with polystyrene PS 158 K example Modulus Tension at Stretching at transparency Haze YI FS Fmax.

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Claims (13)

  1. Mélanges contenant des copolymères séquencés linéaires à base de monomères vinylaromatiques et de diènes de structure


            S1-B1-S2     (I)

    et


            B2-S3     (II)

    ,
    S1 représentant une séquence de monomères vinylaromatiques ayant une masse moléculaire moyenne en nombre Mn dans la plage de 40 000 à 100 000 g/mole,
    S2 et S3 représentant chacun des séquences de monomères vinylaromatiques ayant une masse moléculaire moyenne en nombre Mn dans la plage de 5 000 à 20 000 g/mole,
    B1 et B2 représentent chacun une ou plusieurs séquences de copolymères de diènes et monomères vinylaromatiques ayant une masse moléculaire moyenne en nombre Mn dans la plage de 15 000 à 100 000 g/mole, le rapport monomère vinylaromatique/diène dans les séquences B1 et B2 se situant dans la plage de 0,3 à 1, 5 et le rapport des copolymères séquences (I)/(II) se situant dans la plage de 0,5 à 10.
  2. Mélanges selon la revendication 1, caractérisés en ce que le rapport des copolymères séquencés (I)/(II) se situe dans la plage de 2 à 3.
  3. Mélanges selon la revendication 1 ou 2, caractérisés en ce que le rapport des masses moléculaires moyennes en nombre de S1 à S2 se situe dans la plage de 5 à 8.
  4. Mélanges selon l'une quelconque des revendications 1 à 3, caractérisés en ce que les séquences B1 et B2 représentent chacune une ou plusieurs séquences de copolymères de diènes et monomères vinylaromatique à distribution statistique.
  5. Mélanges selon l'une quelconque des revendications 1 à 4, caractérisés en ce que les masses moléculaires moyennes en nombre Mn de
    S1 se situent dans la plage de 60 000 à 85 000, de S2 et S3 se situent chacune dans la plage de 8 000 à 17 000 g/mole, et de
    B1 et B2 se situent chacune dans la plage de 50 000 à 75 000 g/mole.
  6. Mélanges selon l'une quelconque des revendications 1 à 5, caractérisés en ce que les séquences B1 et B2 se composent chacune de deux séquences de copolymères (B/S)a a et (B/S)b de diènes et monomères vinylaromatiques, le rapport monomère vinylaromatique/diène se situant dans la séquence (B/S)a dans la plage de 1 à 1,5 et dans la séquence (B/S)b dans la plage de 0,3 à 1.
  7. Mélanges selon l'une quelconque des revendications 1 à 6, caractérisés en ce que respectivement les masses moléculaires moyennes en nombre Mn de S2 et S3 et les masses moléculaires moyennes en nombre de B1 et B2 ont la même valeur.
  8. Mélanges selon l'une quelconque des revendications 1 à 7, caractérisés en ce qu'ils contiennent
    5 à 95 % en poids des copolymères séquencés linéaires (I) et (II) et
    95 à 5 % en poids de polystyrène standard ou de polystyrène choc.
  9. Mélanges, prouvant être obtenus par hydrogénation partielle ou totale des mélanges selon l'une quelconque des revendications 1 à 8.
  10. Mélanges selon la revendication 9, caractérisés en ce que le degré d'hydrogénation des motifs monomères vinylaromatiques est d'au moins 90 %.
  11. Mélanges selon la revendication 8, caractérisés en ce que les motifs diène incorporés par polymérisation sont présents sous la forme 1,2-vinyle à raison de plus de 30 %, par rapport à la somme des motifs diène.
  12. Procédé pour la préparation de mélanges selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'on prépare successivement ou dans différents réacteurs les copolymères séquencés (I) et (II) chacun par polymérisation anionique séquentielle de monomères vinylaromatiques et de diènes avec des amorceurs organométalliques à base de métaux alcalins et ensuite on les mélange en un rapport (I) / (II) dans la plage de 0,5 à 10.
  13. Procédé pour la préparation de mélanges selon la revendication 7, caractérisé en ce qu'on prépare simultanément dans un réacteur les copolymères séquencés (I) et (II) par polymérisation anionique séquentielle de monomères vinylaromatiques et de diènes avec des amorceurs organométalliques à base de métaux alcalins par double amorçage, comprenant l'addition dosée conjointe d'amorceur I1 et de monomères vinylaromatiques dans une première étape et addition dosée conjointe d'amorceur I2 et de diènes ou de diènes et de monomères vinylaromatiques dans une deuxième étape, le rapport de la quantité d'amorceur I1 de la première addition dosée à la quantité d'amorceur I2 de la deuxième addition dosée se situant dans la plage de 0, 5 à 10.
EP05025845A 2004-12-10 2005-11-26 Mélanges transparents de copolymères à blocs du type styrène-butadiène Not-in-force EP1669407B1 (fr)

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DE102004059783A DE102004059783A1 (de) 2004-12-10 2004-12-10 Transparente Mischungen linearer Styrol-Butadien-Blockcopolymerer

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EP1669407B1 true EP1669407B1 (fr) 2011-10-12

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US (1) US7470746B2 (fr)
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US20060128890A1 (en) 2006-06-15
EP1669407A1 (fr) 2006-06-14
ATE528354T1 (de) 2011-10-15
JP2006169522A (ja) 2006-06-29
DE102004059783A1 (de) 2006-06-14
US7470746B2 (en) 2008-12-30

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